Caoutchouc-like substances and process of making them.



UNITED STATES PATEN T OFFICE.

HENRY STALAY ARTHUR HOLT, or LunwIGsHAFnn-ou rnn-nnmn, GEnMANY,

ASSIGNOR T BADISCHE ANILIN & SODA FABRIK, or LUDWIGSHAEEN-ON-THE- RHINE, GERMANY, A CORPORATION.

GAO UTCHOUG-LIKE SUBSTANCES AND PROCESS OF MAKING THEM.

No Drawing.

1 0 all whom it may concern:

. In. this way,-large quantities of compounds Be it known that I, HENRYwSTALAY AR- THUR HoL'r, Ph. D.,fcitizen of the British Empire, residing at Ludwigshafen-on-the- Rhine, Germany, have invented new and useful Improvements in Caoutchouc-Like Substances and Process of Making Them, of which the following is a specification.

" It is known that butadiene and its homothe product obtained being insoluble in the. butadiene hydrocarbon and the initial hy-- drocarbon remaining limpid till the whole is changed into the newbody. v

The treatment of the butadiene hydrocarbon with the alkali metal in the presence of carbon dioxid can be carried out in various manners, without departing from my invention. For instance, either a single metal such as sodium may be employed, or mixtures of the alkali metals with one another or with other metals can be employed, and

in some cases, an advantage is secured by using such mlxture. In this specification I include alloys under the term mixtures. It is also often advantageous to make use of the alkali metal in the presence of a solid body, for instance the hydrocarbon may be shaken with the alkali metal in the presence of carbon dioxid and of balls of zinc, glass, clay, porcelain and quartz. In some cases, for instance, when the butadiene hydrocarbon, alkali metal and carbon dioxid are allowed to stand together, a dark colored product is obtained, which I regard as the polymerized product vidcd alkali metal. This dark colored product can also be employed instead of taking fresh alkali metal, in order to bring about polymerization of further quantities of butadiene hydrocarbon in the' presence of carbon dioxid according to my invention.

mixed with finely die Specification of Letters Patent.

Application filed July so, 1913. Serial No. 782,028.

resembling or related to caoutchouc can be obtained with the use of very little sodium or the like.

If the reaction be carried out at a raised temperature, the velocity thereof is often accelerated. My new products are characterized by being white-substances, which are insoluble 1n isoprene, are insoluble in benzene and do not swell when-placed therein, and contain at least 88.15% carbon. i

The following examples will serve toillustrate further the nature of my invention and howlit can be carried into practical effeet, but the invention is not confined to these examples. The parts are by weight.

Examplelz Shake together, at ordinary temperature, one hundred parts of 2.3-dimethyl-lz3-butadiene and five parts of sodium wire in a vessel-filled-with a dry carbon dioxid. After from two,'to three, days the sodium, which has broken up into short pieces, appears to swell and after another three to seven days the dimethyl-butadiene is practically quantitatively converted into a voluminous black 'mass without having 30 passed through a viscous stage." OnQtreating this black mass with water, or alcohol,

'it rapidly becomes pure white and can-be purified from alkali by washing with'water. The process differs from that" which takes place when the treatment is carried out in, the absence of carbon dioxid, as, in the latter case, a reduction of volume takes place and the liquid grows continually more viscous anda different product is obtained.

Example 2: Place one hundred 'parts of isoprene with five parts of sodium, in the form of wire, in a capacious vesselwhich is otherwise filled with carbom dioxid, and

then shake thevessel. After about fourteen i to twenty days, the sodium, which is covered wlth ablack layer, appears to swell and,after a time, a voluminous black mass is obtained without the isoprene passing through a vis cous stage. Introduce this mass into alcohol, whereupon it becomes white, and then wash it with water until it is free from alkali. It is practically insoluble in benzene and isoprene. If the process described in s i this examplebecarried outat a temperature of from forty to fifty degrees centi'grade, the reaction proceeds more quickly and is complete in, say, about tendays'.

Example 3: Pour five hundred partsof 2.3-dimethyl-L3-butadiene over one hundred parts of the'black polymerization product obtained according to the foregoing Example' 1 and allow the mass to stand in an atmosphere of carbon dioxid, until the liquid has disappeared. Q

Example 4:: Polymerize one hundred parts of 2.3-dimethyl-1.3-butadiene withfive parts of sodium in a vessel filled with dry carbondioxid, asdescribed in the forego-" ing Example 1, then add from five hundred to six hundred parts oifresh dry 2.3-dimethyl-IB-butadiene and allow themass ,to

stand, in an atmosphere of carbon dioxid', for from five to six days, when the liquid will have disappeared and the whole have become converted into a voluminous black mass. Repeat the addition of fresh 2.3- dimethyl-.1.3 butadiene once, or several times, as long as the reaction mass is of a dark color. 4

Examplefi: Place one hundred parts of '2.3-dimethyl-l.3-butadiene, five parts of fine sodium Wire and five parts of iron filings in a vessel and drive outthe air by means of-carbon dioxid. Then close the vessel and shake it for from three to seven days until the whole mass is converted into a black voluminous product. This can be freed from alkali metal .by introducing it into Water, alcohol or the like, while at the same time part of the iron is separated mechanically. The remaining iron can be as dissolved away by treatment with hydrochloric acid. Ina similar-.manner, other metals, such for instance as zinc, tin, lead, and nickel, can be employed, and other hydrocarbons of .the butadiene series can be polymerized. .Example 6: Shake, for a few days 'one v hundred parts of 2.3-dimethyl-L3-butadiene with a quantity of liquid, 'or finely powdered solid, sodium amalgam containing about two parts of sodium, in a vessel,'hav-- I ing first replaced the air by an atmosphere of carbon dioxid. When the mass has be= come black and solid, introduce it into water and separate the product, which has turned white, from the mercuryby means of centrif- Y ugalaction. In a similar manner, other 7 sodium alloys, such for example -as lead- In the sodium, can be employed, and'other hydrocarbons of jthe butadieneseries canbe polym ri ed I foregoing examples; sodium can be ,re'plaeed bypotassiunr and similar products can beobtained from butadiene, or homo.

loguesthereoflsuch for example as the hexai dienes, for instance Q-ethyI-LB-butadiene' Ifdesired, the dark colored product obtaijned from any one of theafores'aidhydrocarbons can be employed polymerization of an'yfotherof them.

m ma -7: Grind together, in a adrenalin ball mill, in which the air has been replaced by carbon dioxid, one hundred parts of .isoprene and five parts of metallic sodium, until a dry mass .is obtained. Ordinary temperature may be employed, or the reaction may be carried out at a moderately raised temperature. The light gray product, which is permeated wi'th finely divided glistening sodium, can .be, employed for.

polymerizing a further quantity of isoprene, or it can be introduced into water in order to free it from alkali metal and then be separated from theporcelain balls and dried.

-N ow what I claim is:

1. The process ofv producing substances resembling or related to caoutchouc by,

resembling or related to caoutchouc by shaking a butadiene hydrocarbon with an alkali metal and zinc balls in the presence of carbon dioxid.

5. "The process of producing substances resembling or related tocaoutchouc by treating a butadiene hydrocarbon with analkali -metal in the presence of carbon dioxid, and then, when a dark colored mass has been. ob

' tained, adding a further. quantity of butadiene hydrocarbon,- and allowing polymerization tov proceed, also-in'the presence ofcarbon dioxid.

6. The sub-process of producing {substances resembling or related to 'caoutchouc 'by treating,a butadie'ne hydrocarbon in the presence of carbon dioxid-- with the dark colored substance-produced by acting on a butadiene hydrocarbon with an alkali metal in the presence of carbon *dioxid.

-7. Theprocess ofproducing substances resembling or related to caoutchoue by,

treating a butadiene hydrocarbon in the presence of carbon dioxid with a mixture of an alkalimetal with another metal.

8. The new substances resembling or re- .lated to caoutchouc which can be obtained .b I

aliv metal in the presencejof carbondioxid, which new substances are white and treating a-butadiene hydrocarbon with insoluble in-. i s oprene,- are insoluble in benzene and do not swell when placed therein and contain at least 88.15% carbon. .9. Thenew substance resembling or 'related to caoutchouc which can be obtained by treating isoprene with sodium in the my hand in the presence of two subscribpresence of carbon dioxicllwhich new subing witnesses. stance is White and insolu e in isoprene, is insoluble in benzene and does not swell when HENRY STALAY ARTHUR HOLT 5 placed therein, and contains practically Witnesses:

' 8 8.15%carbon. J. A1320. LLOYD,

In testimony whereof I have hereunto set JOSEPH PFEIFFER. 

